Stabilized poly-alpha-olefin compositions



July 29, 1969 G. .1. Lls'rNER 3,458,471

STABILIZED POLY-'f-OLEFIN COMPOSITIONS Filed July 19, 1967 v 2 Sheets-Sheet l I l I I O l 2 3 A- 5 e 7 9 lo n n2 INVENTOR @Pf-50,? Y /5 rms@ BY HT July Z9, 1969 G. JQ L lsTNER 3,458,471

STABILI ZED POLY-f-OLEFIN COMPOSITIONS Filed July 19, 1967 2 Sheets-Sheet 2 Tll.

Oxygen ATTORNEY United States Patent O U.S. Cl. 26o-45.75 9 Claims ABSTRACT oF THE DISCLOSUREl This invention relates to stabilized poly-a-olefin articles comprising Ipoly-vc-olefins, chlorinated polyphenyl cornpounds, certain ultraviolet light absorbers and combinations of antioxidants. The stabilized poly--olefins have improved resistance to oxidative ydegradation on exposure to sunlight and to weathering.

This is a continuation-in-part of application Ser. No. 341,614 filed Jan. 31, 1964, which is a continuation-inpa-rt of application Ser. No. 293,823 filed July 9, 1963 now U.S. Patent 3,277,046 issued Oct. 4, 1966.

By the term ot-olelins as used herein, applicant means olefins having substantially all of the unsaturation in the a position and further limited to those olefms wherein the resultant polymerizate is a self-supporting structure.

The polymers of a-olefins and like ethylenically unsaturated materials, particularly polyethylene and polypropylene of the low, medium and high density varieties, have many desirable characteristics which make them useful in a wide variety of molded and shaped products. These characteristics include their thermoplastic nature, which allows for easy molding, shaping, extruding fabricating, etc., their inertness and other controllable physical and chemical properties.

Despite these desirable characteristics, thermoplastic poly-ot-olefins have been limited in use in certain areas and have been excluded from others because of their tendency to become brittle, form powder on their surfaces, lose strength and darken in color on exposure to light and weathering as is normally encountered in outdoor uses. As a matte-r of illustration, polypropylene is a useful thermoplastic only because means have been found to provide limited stabilization against oxidative attack, since unstabilized polypropylene oxidizes rapidly at relatively low temperatures.

Thus, moldings, monofilaments, multilaments, iibers, sheets, films and other sections derived from these polymers have a very limited useful life in outdoor applications Where exposure to sunlight and oxygen of the air occurs for prolonged periods of time. In such environments, these polymers degrade very rapidly resulting in virtually complete loss of required mechanical properties such as tensile strength, elongation, tear strength, abrasion resistance, etc. As a consequence, the products derived from the polymers have only very limited utility in a vast range of uses, including shade cloth, seed bed covers, sailcloth, automotive upholstery fabrics, rope and cord, boat covers, construction projects, signs, etc.

Certain additives have been employed in the past to overcome this sunlight degradation. One such treatment is incorporating finely dispersed carbon black particles in the polymer but this of course conveys a black color to any a-rticle so treated. Some of the other substances used also impart dark colors to the polymer or result in opacity, or in other ways impair the properties of the linal product.

Proposals have been made to incorporate various antioxidants and various ultraviolet light-absorbing materials ICC into the polymer, or combinations of these two, but the antioxidants normally employed are rapidly consumed during the ydecomposition of the polymer due to weathering and the ultraviolet absorbents are only active for short durations due to the decomposition of the absorbing material or because they migrate to the surface of the polymer and are volatilized. Furthermore, compatibility of various absorbers and antioxidants with the olefin polymers is very limited.

I have now discovered that poly-a-oleiins can be made more receptive to the addition of stabilizers, i.e., become preconditioned to the acceptance of stabilizers, by the incorporation into the poly-a-olefin of from about 1% to about 30% lby weight of a chlorinated polyphenyl compound having from about 20% to about 70% chlorine by weight.

Thus, this invention includes an easily stabilizable intermediate in the stabilization of poly-a-oleiins which comprises a poly-a-olefin and from about 1% to about 30% by Weight of a chlorinated polyphenyl compound, having f-rom about 20% to about 70% chlorine by weight, selected from the group consisting of chlorinated biphenyl, chlorinated triphenyl and blends of chlorinated biphenyl and chlorinated triphenyl.

By the term easily stabilizable as used herein is meant that the presence of from about 1% to about 30% of the chlorinated polyphenyl compound in the poly-ocoletin insures that effective stabilizer additives, e.g. ultraviolet light absorbers, antioxidants and heat absorbers, will be readily accepted, and readily distributed through the poly-a-olefin in amounts, and to degrees, which have not been possible in the past.

In addition, the chlorinated polyphenyl compound itself contributes to significant reduction in the Oxygen transmission rate exhibited by the poly-a-olefin. Thus, the incorporation of chlorinated polyphenyl into the polya-olefin composition contributes two fold to the reduction in the oxygen transmission rate exhibited by the polymer and thus the oxidative `degradation rate of the polymer, since the gross effectiveness of the effective stabilize-rs is dramatically increased and greater amounts are made compatible with the polymer.

Additionally, distribution of these stabilizers Within the poly-a-oleiin is greatly improved. As a result of these advances the life of the poly-a-olefin is greatly increased since there is far less oxygen absorbed per unit of time.

The term effective stabilizer additives as used herein defines poly-a-olefin compatible ultraviolet light absorbers which block damaging ultraviolet light, heat stabilizers and antioxidants which are poly-a-oletin compatible, which have heat and color stability and which act as peroxide scavengers. The term effective stabilizer additives is also meant to include, by definition, additives which are poly-a-olefin compatible and which have a synergistic effect on the performance of the antioxidants, i.e., combine with the antioxidants to give increased performance. Examples of these additives are di-stearyl and di-lauryl-thiodipropionate and a dialkyl phenol sulfide.

The present discovery includes a stabilized polyoleiinic shaped article comprising a poly-a-olefin, from about 1% to about 30% by weight of a chlorinated polyphenyl compound, having from about 20% to about 70% chlorine by weight, selected from the group consisting of chlorinated biphenyl and chlorinated triphenyl, and from about 0.1% to about 10% by weight of effective stabilizer additives.

The chlorinated polyphenyl compounds which may be used in accordance with the present invention are any of the biphenyl or triphenyl compounds containing from about 20% to 70% by Weight of chlorine or blends of chlorinated biphenyls and triphenyls containing from about 20% to 70% chlorine. Suitable examples of such chlorinated polyphenyl compounds are chlorinated biphenyl containing 60% by weight chlorine, chlorinated triphenyl containing 60% by weight chlorine, and a blend of chlorinated triphenyl and chlorinated biphenyl containing 65% by weight chlorine, etc. With less than 20% by weight chlorine in the polyphenyl compound, there is substantially no significant reduction of the oxygen transmission rate exhibited by the poly-a-olefin to which it has been added, and the incorporation of additional quantities of effective stabilizers is not made possible.

The chlorinated polyphenyl compounds are incorporated into the polymer in an amount suicient to provide from about 1% to about 30% or more by weight, in the final polymer; 5% to 25% being preferred. If less than about 1% of the chlorinated polyphenyl is used in the compositions of the present invention there is little enhancement of the stability of the polyolefin. Whereas, if more than about 30% of the chlorinated polyphenyl is used the additives in the resultant polyolefin material may bloom excessively at service temperatures. In addition to markedly increasing the resistance to degradation of the polymeric composition the chlorinated polyphenyl compounds increase the melt flow range of the polymer during extrusion.

The presence of the chlorinated polyphenyl in the polya-olefin enables or facilitates the addition of stabilizers into the poly-a-olens in amounts which have not been possible before with any beneficial effect, since prior to this invention the stabilizers have just not been readily accepted by the poly-a-olefin in more than very minor amounts which are considerably below the amounts now made possible. Also the distribution of that stabilizer that was incorporated into the polymer was not satisfactory in most cases. By reason of the instant invention, the poly-ot-oleiins can be made receptive to certain stabilizer additives in amounts sufiicient to greatly improve their resistance to heat and ultraviolet light degradation. Additionally, the dispersion of these additives within the polymer is very good; therefore, uniform performance is effected.

The improved poly-a-oleiins of the present invention retain a considerable portion of their tensile strength for long periods of time. They also retain a portion of their elongation after lengthy exposures to sun and weather. Furthermore, the improved compositions of the present invention stop powdering on the surface of poly-a-olefins which are exposed to sun and weather.

The effective stabilizer additives have been defined quite generally. In the preferred embodiment of this invention the presence of an antioxidant, an ultraviolet light absorber and a member of the group which combines with the antioxidant to give improved performance are all present together with the chlorinated polyphenyl compound; however, due to the nature of the chlorinated polyphenyl compound and to the increased receptivity to stabilizer additives which it effects in the poly-a-olefins, the presence of all three of these effective stabilizer additives is not necessary in order to obtain improved results. If only heat resistance is desired, the presence of two, or even one, provided the chlorinated polyphenyl is there to condition the poly-a-olelin, will effect results superior to those which presently exist with respect to heat and ultraviolet light degradation of the polymer; however, the most improvement in these features is evidenced when a member of each of the constituents of the effective stabilizer additives is present.

In considering the ultraviolet absorbers, concern is manifested in that portion of the sunlight spectrum, i.e. the ultraviolet energy, which is suiciently powerful to rupture chemical bonds or, in other words, sufiiciently powerful to cause photochemical degradation of the polyoleiinic shaped article. In the system of this invention the ultraviolet absorbers must be limited to those which are compatible with the particular poly-a-olefins defined herein. These are represented by p-octylphenyl 'salicylate, 2 hydroxy 4 n octoxybenzophenone; 2-

ethylhexyl 2 cyano 3,3' diphenyl acrylate; [2,2- thiobis (4 t octylphenolato)] n butylamine Nickel (11); and tert-butyl salicylate. The ultraviolet absorber may be present in an amount from about 0.0% to about 10% by weight in the finished product. When the existence of the effect of the ultraviolet light absorber is desired, from about 0.25% to about 5% by weight are acceptable limitations. If no ultraviolet light absorber is present in the system, the end results while considerably improved insofar as the resistance to heat and light degradation of the poly-a-olefin is concerned, are not as greatly improved as they are when the ultraviolet light absorber is present.

The antioxidants contemplated in the system of this invention must also be compatible with the poly-a-olefins at extrusion temperatures and at service temperatures, i.e., they must be nonextruding, but they must also have sufiicient heat stability at extrusion temperature to permit the extrusion of the polyolefin composition. They must also possess color stability such that there is little or no color change during, or after, extrusion or during the reasonable lift of the polymer. They must also possess excellent water resistance so that moisture will not leach it from the final product, thereby destroying the tensile strength and oxidation resistance which are desired. Representative of antioxidants which fall within this definition are 2,6 di tertiarybutyl p cresol; i.e., dioctadecyl 3,5 di t butyl 4 hydroxybenzylphosphonate; 2,4-bis-(n-octylthio) 6 (3,5 di t butyl- 4 hydroxyanilino) 1,3,5 triazine; 2,4 bis (3,5 dit butyl- 4 hydroxyphenoxy) 6 (n octylthio) 1,3,5- triazine; octadecyl 3 (3,5 di t butyl 4 hydroxyphenyl) propionate; and dioctadecyl 3,5 di t butyl- 4 hydroxybenzylphosphate Santanox, i.e 4,4' thiobis( 3 methyl 6 tbutylphenol) Topanol C.A., a 3:1 condensate of 3methyl, 6-tertiary butyl-phenyl with crotonaldehyde, Nonox WSP and Nonox CL two phenolic antioxidants 2246 and 425 2,2' methylene (bis- 4 methyl 6 t butylphenol), and 2,2' methylene (bis 4 ethyl 6 t butylphenol) respectively; 703 i.e., 2,6 di t butyl a dimethylamino p cresol; 2,4,5 tri hydroxybutyrophenone; mutylated hydroxytoluene.

These primary antioxidants must be present in amounts sufficient to insure a content of from about 0.05 to about 5% by weight, in the final polymer; however, within the more commercial aspects of the present invention the use of from about 0.25 to about 2% by weight is contemplated.

The fourth additive, or secondary antioxidant, such as a phenol-sulfur organic, is represented by di-laurylthiodipropionate, distearyl thiodipropionate, or Sterobane 20, a modified polymeric thioester, in an amount suicient to provide from about 0.05% to about 2% by weight in the final polymer. From about 0.1% to about 0.5% by weight, is preferred. This particular additive is necessary since it is synergistically reactive with the antioxidant and it imparts heat stability to the final polya-olelinic shaped article, i.e., a film, filament, extrudate or molded article of manufacture.

It is believed that the primary antioxidant scavenges the active oxygen while the secondary antioxidant decomposes the hydroperoxides which form as a result of primary oxidation.

Heat stabilizers compatible with the poly--olefn and which exhibit good resistance to heat during extrusion may also be added to the system provided that they are non-migrating.

The easily stabilizable intermediates of this invention are prepared by:

(A) Mixing a particulate poly-a-oleiin and a chlorinated polyphenyl solution in an amount sufficient to provide from about 1% to about 30% by weight addon of chlorinated polyphenyl, and

(B) Baking said mixture at a temperature of from about 150 F. to about 300 F. for a period of from about 1/2 hour to about 8 hours whereby the poly-aolefin substantially uniformly absorbs said chlorinated polyphenyl composition. I

Of course, this may also be accomplished by coating a poly-a-olen shaped article with suicient chlorinated polyphenyl to insure from about 1% to about 30% by weight add-on followed by the baking step.

Polyoleiinic shaped articles stabilized as to heat and ultraviolet light degradation and having improved feel and pleasing hand without sacrifice of the desirable strength properties are provided by the method which comprises:

(A) Dissolving (a) from about 0.0% to about 5% by weight of a poly--olenic compatible ultraviolet absorber composition, (b) from about 0.05% to 2% by weight of a poly-a-olenic compatible antioxidant exhibiting heat and color stability, and (c) from about 0.05% to about 2% by weight of a member selected from the group consisting of a dialkyl phenol sulfide, dilauryl thiodipropionate, and di-stearyl thiodipropionate in a chlorinated polyphenyl compound to form a solution,

(B) Mixing said solution with a poly-a-olefin polymer,

(C) Heating said mixture to a temperature of from about 150 F. to about 300 F. for a period of from about 1/2 hour to about 8 hours whereby the poly-a-olen uniformly absorbs said solution, and

(D) Forming said mixture into a shaped article, said article having improved resistance to both heat and ultraviolet light degradation.

The heating step, i.e., step C above, is of paramount importance in either the process for preparing the intermediate or in the process for preparing, at one time the stabilized polyoleiin, since the absence of this heating or baking of the mixture at this stage will effect unsatisfactory results in that the distribution of the additives in the polymer will not be complete. This would affect the uniformity of performance to a point where the polymer composition is not extrudable in an acceptable fashion because of plating out. Also, in instances where some extrusion is possible, the performance of the -iinal product would be highly variable since, as stated, the additives are not uniformly distributed throughout the polymer.

Below 150 F. the absorption of the additives into the polymer is very slow and therefore impracticable. At temperatures higher than about 300 F., although absorption is very rapid, softening or premature melting of the polymer takes place. Of course it is realized that this maximum temperature may fluctuate depending upon the poly-a-oleiin used.

In extruding poly-a-olen materials to form` filaments, the poly--olen should have a narrow range of melt ow rate in order to obtain continuous, uniform formation of the lament and to preclude lumping. Usually for polypropylene the melt flow rate will be around 4.0 and will vary very little from this figure. However, when the compositions of the present invention are incorporated in the poly-m-oleiin material the criticality of the melt flow rate is removed and poly-a-olein material having varying melt ow rates and broad ranges of melt ilow rates may be extruded continuously and uniformly into filaments. For example, I have found that I may extrude polypropylene having a melt flow rate ranging from 3 to 7 into commercially acceptable filament-s when the composition of the present invention is incorporated with the polypropylene prior to extrusion.

As previously mentioned, poly-a-oleiinic additives very often reduce the clarity of the olenic material and make it milky or opaque. However, when using the compositions of the present invention the original clarity poly-- olefinic materials may be substantially preserved by the addition of up to 5% of mineral oil to the compositions of the present invention. Addition of such minor amounts of mineral oil produces a clear poly-a-olen material which maintains its clarity even after lengthy exposures to sun and weather. I have established that if mineral oil is added to a polyolelinic system without the inclusion of the additives described herein, it, the mineral oil, is compatible with the polyolefinic material only when it is hot or thermoplastic; however, it separates out, i.e., it exudes from the polymer on cooling and solidication of the polymer composition, thus not only resulting in a milky colored polymer but also reducing the tensile strength of the polymer.

The incorporation of the additives into the polymer can be done by any one of several methods that insure uniform distribution. For example, if the chlorinated polyphenyl compound is a liquid the other compounds may be dissolved in the chlorinated polyphenyl compound and the combinations then mixed with warm polymer, or if all the compounds are solids they may be mixed by hot milling such as a two-roll heated mill or by melting of the additives together and coating this mixture uniformly on the small pellet particles of the warm polymer, allowing the mixture to cool after thorough mixing, or by dissolving the additives in solvents such as xylene and toluene and then mixing with the polymer in powder, flake or pellet form. Other methodsl of blending the components may also be employed, such as extrusion mixing, etc.

In most instances it is difficult to uniformly disperse additives in the poly-zx-oleiin polymer. It is believed that this is caused lby the fact that a true solution is not formed but that the additive molecules simply disperse themselves, at random, in and amongst the crystalline structure of the olefin.

I have discovered that the compositions of the present invention may also be readily incorporated into poly-aolefin polymers with extreme uniformity by iirst dissolving (A) from about 0.0% to about 10% by Weight of a poly-a-olen compatible ultraviolet light absorber, (B) from about 0.05% to about 5% by weight of a poly-- olelin compatible primary antioxidant exhibiting heat and color stability, and (C) from about 0.05 to about 5% by weight of a secondary antioxidant selected from the group consisting of a dialkyl phenol sulfide, di-lauryl thiodipropionate and di-stearyl thiodipropionate, into (D) from about 1% to about 30% by weight of a warm chlorinated polyphenyl compound, having from about 20% to about 70% chlorine by weight, selected from the group consisting of chlorinated biphenyl, chlorinated triphenyl and blends of chlorinated biphenyl and chlorinated triphenyl. An organic solvent compatible with the system may be added to facilitate ease of application of this coating composition onto the poly-a-olelin structure. The chlorinated polyphenyl solution is poured over the polya-olen polymer which has been prewarmed to a temperature of from about F. to about 275 F. or higher but not as high as the melting point of the olen polymer. The olefin polymer coated with the chlorinated polyphenyl solution is baked at a temperature of from about F. to 300 F. for a period of from about 1/2 hour to 8 hours or more and the poly-a-olefin polymer uniformly absorbs the chlorinated polyphenyl solution. The amount of add-on of the coating composition should be within the range of 1% to 30%, or preferably within the range of 5% to 25%, measured in terms of the amount of chlorinated polyphenyl constituent taken up or absorbed by the poly-a-oleiin composition.

The quantity of each of the additives to be employed will in general depend upon the amount of stability required. Certain important limits have been defined to obtain the maximum effect, however.

The normal procedure in evaluating the light stability of olenic materials has been to expose samples of iilm, lament, fabric, or other forms to outdoor sunlight and weathering in a location where the annulal amount of sunlight is very high, such as in southern Florida or Arizona. Thus, measurement of exposure used herein is directly related to exposure to weather conditions found in these two states.

Although the principles of the present invention are being described with particular reference to isotactic polypropylene as the preferred poly-a-oletin, it is to be appreciated that the practice of the invention is beneficial to other poly-a-olens, notably polyethylene. It is also to be noted that the invention is applicable to copolymers or polyallomers of poly-a-oleiins either of different species of the same poly-a-oleiin, such as a blend of low molecular weight polyethylene and high molecular weight polyethylene or of different copoly-a-olens such as polyethylene-polypropylene, polyethylene-polybutylene, etc. In its broader aspects the invention is thus applicable to any poly-a-olen or to mixtures of or combinations thereof in the form of blends, copolymers, polyallomers, etc., which are susceptible to light-induced degradation.

The invention will be more readily understood by referring to the accompanying drawings wherein:

FIG. I is a plot of filaments exposed to sunlight,

FIG. II records the oxygen transmission rate of films containing from to 20% chlorinated polyphenyl compound, and

FIG. III records a comparison of the retained tensile strength and elongation of two polypropylene filaments, both containing a U.V. stabilizer and primary and secondary antioxidants but only one sample, i.e. E, containing a chlorinated polyphenyl compound.

With particular reference to FIG. 1, there is shown a graph wherein the percent retained tensile strength of monofilaments is plotted against the equivalent months of exposure to weather in Arizona or Florida. In all instances the filament size and other characteristics except additives are the same, and the filaments are tested under fabric conditions at temperatures of 75 C. to 80 C. Plotted on the graph are the determinations for (A) a 100% polypropylene filament, (B) a polypropylene filament stabilized with a composition of p-octylphenyl salicylate, di-lauryl-thiodipropionate, and 2,6-di-tertiarybutyl-p-cresol, and (C) a polypropylene filament containing a composition of the present invention, i.e., p-octylphenyl salicylate, di-lauryl thiodipropionate, 2,6-di-tertiarylbutyl-p-cresol and chlorinated biphenyl. As can be seen from the graph, not only does the composition of the present invention, i.e. composition (C), drastically increase the percent retained tensile strength of the polypropylene filament after considerable exposure, but in fact completely changes the slope and configuration of the curve. Polypropylene by itself degrades extremely rapidly after 2 to 3 months exposure and polypropylene containing some stabilizer degrades very rapidly during the 6th to 9th or 10th month of exposure. The filaments of the present invention, even after l0 months of exposure, degrade slowly and maintain a higher percent of their tensile strength after a considerably longer exposure than previous type stabilized polyolen filaments.

FIGS. II and III will be examined in greater detail in connection with Examples 19 and 20 which follow.

The invention will be further illustrated in greater detail by the following specific examples. It should be understood, however, that although these examples may describe in particular detail some of the more specific features of the invention they are given primarily for purposes of illustration and the invention in its broader aspects is not to be construed as limited thereto.

Example 1 A mixture of 1 pound of p-octylphenyl salicylate, -1/2 pound 2,6-di-tertiarybutyl-p-cresol and 1/2 pound dilauryl thiodipropionate is melted on a steam bath and then tumbled with 100 pounds of isotactic polypropylene pellets (a general purpose U.V.unstabilized extrusion resin) which is warmed to about 120 F. The tumbled material is allowed to cool to room temperature. The pellets,

uniformly coated with the additive mixture, are then baked at 250 F. for 2 hours and extruded through a 1inch laboratory extruder into 19 x 85 mil size monolaments, quenched in cold water, and oriented 6:1 to give 9 x 30 mil size monolilaments. The monofilaments are exposed to an equivalent of 8 months Florida exposure, 9 months Florida exposure and 10 months Florida exposure. At the end of each period the monolaments are tested to determine the retained tensile strength as a percentage of the equivalent original tensile strength. After 8v months exposure the retained tensile strength is 42%, after 10 months it is approximately 15%. After 12.5 months it failed.

Example 2 A mixture of 1 pound of (A) p-octylphenyl salicylate, 1/z pound (B) 2,6-di-tertiarybutyl-p-cresol and 1/2 pound (C) di-lauryl thiodipropionate is dissolved in 10 pounds of warm (D) chlorinated biphenyl containing 60% by Weight chlorine. pounds of isotactic polypropylene pellets are warmed to about F. and the above mixture poured over the heated pellets with mixing to coat each pellet. The coated pellets are heated for two 2 hours at a temperature of 220 F. and the chlorinated biphenyl solution is uniformly absorbed by the polypropylene pellets. The material is allowed to cool to room temperature and the pellets obtained are dry and free flowing. The pellets are extruded as described in Example 1 to form 9 x 30 mil size monofilaments. The monofilaments are exposed to an equivalent of 8 months Florida exposure, 9 months Florida exposure and l0 months Florida exposure. At the end of this period the monofilaments are tested to determine the retained tensile strength as a percentage of the original tensile strength. The retained tensile strength after 8 months exposure is 53%, after 9 months exposure it is 48%, and afterI 10 months exposure it is 45%. In this instance the composition of the present invention after 8 months equivalent exposure retained approximately the same amount of tensile strength as did the composition of Example l. After 9, 10 and more months of exposure the decrease in retained tensile is gradual while in the composition of Example 1 the retained -tensile of the filament after 10 months equivalent exposure is virtually nil.

The filament of this example is also tested for percent retained elongation after 9 months equivalent Florida exposure and is found to retain 42% of its original elongation.

Example 3 The procedure set forth in Example 2 is followed with the exception that the mixture contains 2 pounds poctylphenyl salicylate, 1 pound 2,6-di-tertiarybutyl-pcresol, 1/2 pound di-lauryl thiodipropionate, and l0 pounds of the chlorinated biphenyl and 100 pounds of polypropylene pellets. The extruded monoflaments are tested after 8, 9 and 10 months equivalent exposure. The retained tensile strength is found to be 58% after 8 months, 56% after 9 months, and 53% after 10 months. After 9 months equivalent exposure the percent retained elongation of this filament is found to be 45%.

Example 4 l0 pounds of chlorinated biphenyl containing 60% by weight chlorine is warmed and mixed with 100 pounds isotactic polypropylene pellets. The mixture is heated and extruded to form a 9 x 30 mil monolament as described in Example 2. The extruded monolilament is tested after 8 and 10 months equivalent exposure and the retained tensile is found to be 17% after 8 months and 8% after 10 months. The percent of retained elongation of this filament after l0 months equivalent exposure is found to be only 4%.

Having reference to FIG. I, it is noted that line A records the exposure of 100% polypropylene filaments exposed to weather in Florida and Arizona. After about 9 10 6.8 months of such exposure the percent retained tensile Following the procedure of Example 2, the following strength is zero. Thus, the presence of chlorinated biexamples were performed wherein the constituent parts phenyl is shown, by this Example 4, to increase the U.V. of the stabilizing composition are designated by the letters resistance of the polypropylene signiiicantly. This is in A, B, C and D which correspond to the same category addition to permitting the incorporation of greater of constituents having like letter designations in Example amounts of U.V. absorbers, antioxidants, etc. which is 2. All weights are given in parts by weight as compared shown (line C of FIG. C) to very greatly increase the to the total weight of the polymeric mixture.

TABLE I Percent retained tensile, months- Ex. Poly-a-olefin (A) (B) (C) (D) 8 10 12. 5

9 500 parts of isotactic 5 parts p-octylphenyl 2.5 parts 2, -ditertiary- 2.5 parts di-laurylthio- 50 parts chlori- 54 48 44 polypropylene salicylate (OPS). butyl-p-cresol dipropionate nated biphenyLl pellets. (DBPC). (DLTDP) phenyLl 10 do do 5.0 parts (DBPC) 5.0 parts (DLTDP) .do 40 38 25 11 do ..5.0 parts U.V. 531 1.0 parts (DBPC) 1.0 parts distearyld 28 thiodiropionate (DST P). 12 do do 1.0 trytwTopanol 1.0 partsSterobane do 63 38 13 do 2.5 parts Zethylhexyl-Z- 2.5 parts DBPC- 2.5 parts DLTDP do 55 29 cyano-S, 3dipheny1 acrylate.

1 Containing 60% by weight chlorine.

samples resistance to oxidation destruction and thus sig- Example 14 mcantly Increase lts comma-mal me A- mixture of grams of p-octylphenyl salicylate, 2O

Example 5 30 grams of 2,6-di-tertiarybutyl-p-cresol and 10 grams of di- The procedure set forth in Example 2 is followed with lauryi thiodfiropionate is fiiisolved in 1200 .grams of the exception that 4.5 pounds p-octylphenyl salicylate, 2 plgrlgedr ghsg lomlnegog bylwtgtilt ggg; pounds 2,6-di-tertiarybutyl-p-cresol, 3 pounds di-lauryl m .1. g a y ne a 5.0 Ve n thiodipropionate, and 20 pounds chlorinated triphenyl to f.a.c1 nate the ease olf apphcatlon thls .coatmg com' containing by weight chlorine are mixed with 100 35 Pt olpgy ulsesllelssfatgl lasisb pounds of isotactic polypropylene pellets and extruded. lersed in thi Solutio] removed and baked at '250 F The extruded monolaments are tested after 8 and 10 s for 5 minutes. This immersion and baking is once remonths equivalent exposure and the retained tensile d Th d ,7 h 1 d strengths are found to be 60% after 8 months and 56% peate e percent. a .d'on 1S 5'3 D T e regu tant .come

ft 10 nth 40 polypropylene fabric is then exposed to the equivalent a er m0 s' of 8.3 months of sunlight and heat in Arizona and the Example 6 fabric remained intact. The procedure set forth in Example 2 is followed with Example 15 the exception that 1/2 pound p-octylphenyl salicylate, M: A mixture of 15 parts of p octylphenyl salicylate 2.5

ound 2,6-di-tertia -but l- -cresol, 1A pound di-lauryl n hiodipropionate arnyd 7 ypriunds of a mixture of chlo- 45 parts .sterbane 20. and 25 parts 26`d1'tertlaiybutyl'1i' rimmed bi henyl and chlorinated triphenyl containing cresol 1s dissolved in 150 parts of Warm chlorinated biby wleight chlorine are mixed with 100 pounds of phenyl contammg 60% by Welght chlorine'. 50.0 parts of Profax 6623 a aked polypropylene resin is warmed isotactic polypropylene pellets and extruded. The exto about 120., F and the above mixture is poured over truded monoiilaments are tested'after 8 and 10 months 50 the heated resin flakes. The coated flakes are heated equivalent exposure and the retained tensile strengths are for two (2) hours at a temperature of about 220., F and foungl to be 51% after 8 months and 42% after 10 the chlorinated biphenyl solution is uniformly absorbed mon s E 1 7 by the polypropylene akes. The material is allowed to Xamp e cool to room temperature and the akes obtained are dry A base resin of a U.V. stabilized polyethylene-poly- 55 and individually unrestrained. The ilakes are extruded propylene-polyallomer, which is a block copolymer of following the procedure of Example l to form 9 x 30 mil stereoregular ethylene units distributed through isotactic size monolaments. The monofilaments are exposed to polypropylene, is extruded into 9 x 30 mil diameter monoan equivalent of 6.9 months, 10 months and 12 months iilaments without the addition of any stabilizing addi- Florida, exposure. At the end of these periods the monotives. At the end of 8 months equivalent exposure to 60 filaments were tested to determine the retained tensile Arizona heat and sunlight, the retained tensile strength strength as a percentage of the original tensile strength. of a monoiilament is determined to be less than 4% of After 6.9 months the retained tensile was 88%, after the original tensile strength and the retained elongation is 10 months 80% and after l2 months 79%. The percent found to be less than 8% of the original elongation. This retained elongation over the same periods was 69%, 59%

is a complete failure of the filament. 65 and 53% respectively. A control run concurrently re- Example 8 flected 15% retained tensile and 14% retained elongation after 6.9 months. The procedure of Example 2 is followed with the ex- Example 16 ception that 100 pounds of a polyethylene-polypropylenepolyallomer is substituted for the isotactic polypropylene. Example 15 was repeated with the lone exception that The extruded monolarnents are tested after 8, 9 and 10 Z-ethylhexyl-Z-cyano-S,3'diphenyl acrylate was substimonths equivalent exposure and the retained tensile after tuted for p-octylphenyl salicylate. Monolaments were 8 months is 62%, after 9 months it is 56% and after 10 prepared and tested over the same time period under months it is 52%, as contrasted to the 4% value obtained equivalent conditions. After 6.9 months the reta-ined tenfor the base resin. Sile was 86%, after 10 months 82% and after 12 months 76%. The retained elongation over the same periods was 73%, 63% andV 57% respectively.

Example 17 A mixture of parts p-octylphenyl salicylate, 2.5 parts of 2,6-di-tertiarybutyl-p-cresol and 2.5 parts di-lauryl TABLE 1I.-SUMM ARY OF TEST RESULTS PercentIBy Weight Chlorinated Polypllenyl Compound in Thickness Sample Samp Average Individual Values Surface Appearance (Inches) 1 0% 155 151,155 0.0041 II 5% chlorinated biphenyl contauung 60% by weight chlor1ne 140 136, 13 o. 0045 III chlorinated biphenyl containing 60% by weight cl1lorine 135 130, 14 do. 0. 0048 IV.- chlorinated b1phenyl containing 00% by welght chlorine 145 143, 146 Slight Bloom 0. 0040 V chlorinated biphenyl contammg 60% by weight cl1lorine 130 134,129 N oticeable Bloom... 0. 0046 thiodipropionate is dissolved in 150 parts of warm chlorn- Example 20 ated biphenyl containing 60% by weight chlorine. 500 parts of Avisun X-100, a polypropylene resin is warmed to 120 F. and the procedure of Example 15 is followed. The retained tensile of the monoiilaments was measured over periods of 8 months, 10 months and 12.5 months and found to be 54%, 48% and 44%. The retained elongation measured over the same periods was found to be 50%, 41% and 36% respectively. A control of Avisun X-100 failed at 8 months.

Example 18 Example 17 was repeated with the exception that the amount of p-octylphenyl salicylate present was 2.5 parts and the amount of di-lauryl thiodipropionate present was 5 parts. Measurements of the monoiilaments was taken over the same time period with the resultant retained -tensile measured at 54%, 52% and 42% respectively and the retained elongation measured at 39%, 35% and 30% respectively.

Example 19 Six film samples are prepared from compositions I through V. Composition I contained 100% by weight isotactic polypropylene pellets designated 6501 and which is a general purpose U.V.-unstabilized extrusion resin. Compositions II through V contained given amounts of this isotactic polypropylene composition plus varying percentages (as given in Table II) by weight, based on the total weight of the composition, of chlorinated biphenyl containing 60% by weight chlorine.

The films for samples II through V are each prepared by blending in a Hobart Planetary Mixer, Profax 6501 unstabilized polypropylene tiake resin with Aroclor 1260 chlorinated biphenyl at a temperature of 450 F. using a 3.2511 compression ratio screw with 12 sections of feed, 6 sections of transitions and 6 sections of metering tlights. A split film die was used and each of the lms were extruded into a water quench tank and taken up on a roll at 121/2 feet per minute.

Each of the film samples, i.e. I through V, measured 4% x 10% and the gas transmission rate, using standard welding grade oxygen as the gas, was determined following the ASTM D1434-63 test procedure. The gas transmission testing was performed on a DeBell & Richardson, Inc. Gas Transmission Tester, Model No. 4, which utilized the Dow Cell pressure change detection unit specified in ASTM D1434-63 and using the given ASTM test procedure. Duplicate determinations were made at 73i2 F.

With reference to both Table II and the graph presented in FIG. II which plots a fitted curve representing the oxygen transmission rates for each of the samples I through V, it is readily apparent that an increase in the amount of chlorinated polyphenyl compound contributes significantly to a reduction in the oxygen transmission Following the procedure of Example 1, the following compositions E and F, each containing tive members, is prepared. (All percentages by weight are based on the total weight of the particular composition.) The U.V. absorber is Z-hydroxy-4-n-octoxybenzophenol, the chlorinated polyphenyl compound is chlorinated biphenyl containing 60% by weight chlorine and the polypropylene is unstabilized isotactic polypropylene.

1The primary antioxidant is 0.3% by weight Ionol and the secondary lantioxidant is 0.3% by weight DLTDP. In all instances this column defines a combination of 0.3% by Weight each of the secondary antioxidant d-lauryl-thiodipropionate and the primary antioxidant 2,6-ditertiarybutylp-cresol, respectively.

Each of the samples is extruded into 19 x 85 mil monotlilaments, quenched in cold water and oriented 6:1 to give 9 x 30 mil monolaments. Each of these monotilaments is simultaneously exposed to Florida sunlight for a continuous period of 12 months after which the retained elongation and tensile strength of each is measured on our Instron Model TM. The average of each is plotted on the graph presented via FIG. III. The comparative results are dramatic and self-explanatory. The increase in U.V. resistance in the sample containing the chlorinated polyphenyl is certainly significant.

Although several specific examples of the inventive concept have been described the same should not be construed as limited thereby nor to the specific features mentioned therein but to include various other equivalent features as set forth in the claims appended hereto. It is understood that any suitable changes, modifications and variations may be made without departing from the spirit and scope of the invention.

What is claimed is:

1. A stabilized poly-a-olen shaped article comprising a poly-a-olen, from about 1% to about 30% by weight of a chlorinated polyphenyl compound, having from about 20% to about 70% chlorine by weight, from about 0% to about 10% by weight of an ultraviolet light absorber selected from the group consisting of a 2-hydroxy-4-noctoxybenzophenone; 2etl1ylhexyl2cyano3,3diphenyl acrylate; (2,2thiobis(4-t-octyl-phenolate))n-butylamne nickel (II); and tert butyl salicylate from about 0.05% to about 5% by weight of a primary antioxidant selected from the group consisting of 2,6di-tertiarybutyl-pcresol; 2,4-bis-(n-octylthio)-6(3,5ditbutyl4 hydroxyanilino) 1,3,5-triazine; 2,4-bis-(3,5-di-t-butyl-4-hydroxyphenoxy)- 6-(n-octylthio)1,3,5triazine; octadecy1-3-(3,5-di-t-butyl- 4-hydroxyphenyl) propionate; and dioctadecyl3,5dit buty1-4-hydroxybenzyl phosphonate and from about 0.05 to about 2% by weight of a secondary antioxidant selected from the group consisting of di-lauryl-thiodipropionate; di-stearyl-thiodipropionate and a dialkyl phenol sulde.

2. The shaped article of claim 1 in filament form.

3. The shaped article of claim 1 wherein the poly-a-oler'in is selected from the group consisting of polypropylene, polyethylene and a copolymer of polypropylene and polyethylene.

4. The article of claim 1 wherein said chlorinated polyphenyl compound is selected from the group consisting of chlorinated biphenyl, chlorinated triphenyl and blends of chlorinated biphenyl and chlorinated triphenyl.

5. The article of claim 1 wherein said chloriated polyphenyl compound is present in from about 5% to about 25% by weight.

6. The article of claim 1 wherein said ultraviolet light absorber is present in an amount of from about 0.25% to about 5% by weight, said primary antioxidant is present in an amount of from about 0.25% to about 2% by 14 weight and said secondary antioxidant is present in an amount of from about 0.1% to about 0.5% by weight.

7. The article of claim 6 in iilament form.

8. The article of claim 6 wherein said chlorinated polyphenyl compound is selected from the group consisting of chlorinated biphenyl, chlorinated triphenyl and blends of chlorinated biphenyl and chlorinated triphenyl.

9. 'I'he article of claim 6 wherein said poly-a-olen is selected from the group consisting of polypropylene, polyethylene and a copolymer of polypropylene and polyethylene.

References Cited UNITED STATES PATENTS 3,277,046 10/ 1966 Lstner 260-45.85 2,669,521 2/1954 Bierly 260-45.7 3,033,814 5/ 1962 Tholstrup 260-45 .85 3,180,885 4/ 1965 Nentwig 260-45.85 3,215,725 11/ 1965 Strobel et al. 260-45.85 3,255,136 6/ 1966 Hecker 260-45 .85

FOREIGN PATENTS 1,028,723 4/ 1958 Germany.

DONALD E. CZAJA, Primary Examiner J. P. HOKE, Assistant Examiner U.S. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,458,471 July 29, 196

Gregory J. Listner It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 23, "lift" should read life line 43, "mutylated" should read butylated Column 5,4 line 5l, after "polymer" insert mass Column 6 line 74, "annulal" should read annual Columns 9 and l0, Table I, in Example l0, under (A) the ditto should be a blank and under (D) the "phenyLl", second occurrence, should be canceled. Column 13, line 23, "chloriated" should read chlorinated Signed and sealed this 14th day of April 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer 

